Marine diesel cylinder lubricant oil compositions

ABSTRACT

Disclosed herein are marine diesel cylinder lubricating oil compositions comprising (a) a major amount of one or more Group II basestocks, and (b) a detergent composition comprising (i) one or more alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid having a total base number (TBN) greater than 250, and (ii) one or more high overbased alkyl aromatic sulfonic acids or salts thereof; wherein the aromatic moiety of the alkyl aromatic sulfonic acids or salts thereof contains no hydroxyl groups; and wherein the marine diesel cylinder lubricating oil composition has a TBN of about 5 to about 120.

PRIORITY

This application claims the benefit under 35 U.S.C. § 119 to ProvisionalApplication Ser. No. 62/076,309, filed on Nov. 6, 2014, the contents ofwhich are incorporated by reference herein.

BACKGROUND OF THE INVENTION 1. Technical Field

The present invention generally relates to a marine diesel cylinderlubricating oil composition, in particular, for lubricating a marinetwo-stroke crosshead diesel cylinder engine.

2. Description of the Related Art

In the not so distant past, rapidly escalating energy costs,particularly those incurred in distilling crude oil and liquidpetroleum, became burdensome to the users of transportation fuels, suchas owners and operators of seagoing ships. In response, those users havesteered their operations away from steam turbine propulsion units infavor of large marine diesel engines that are more fuel efficient.Diesel engines may generally be classified as low-speed, medium-speed,or high-speed engines, with the low-speed variety being used for thelargest, deep shaft marine vessels and certain other industrialapplications.

Low-speed diesel engines are unique in size and method of operation. Theengines themselves are massive, the larger units may approach 200 tonsin weight and upward of 10 feet in length and 45 feet in height. Theoutput of these engines can reach as high as 100,000 brake horsepowerwith engine revolutions of 60 to about 200 revolutions per minute. Theyare typically of crosshead design and operate on the two-stroke cycle.In addition, these engines usually operate on residual fuels, but somemay also operate on distillate fuels that contain little or no residue.

Medium-speed engines, on the other hand, typically operate in the rangeof about 250 to about 1100 rpm and may operate on either the four-strokeor the two-stroke cycle. These engines can be of trunk piston design oroccasionally of crosshead design. They usually operate on residualfuels, just like the low-speed diesel engines, but some may also operateon distillate fuels that contain little or no residue. These engines canalso be used for propulsion, ancillary applications or both on deep-seavessels.

Low- and medium-speed diesel engines are also extensively used in powerplant operations. A low- or medium-speed diesel engine that operates onthe two-stroke cycle is typically a direct-coupled and direct-reversingengine of crosshead construction, with a diaphragm and one or morestuffing boxes separating the power cylinders from the crankcase toprevent combustion products from entering the crankcase and mixing withthe crankcase oil. The notable complete separation of the crankcase fromthe combustion zone has led persons skilled in the art to lubricate thecombustion chamber and the crankcase with different lubricating oils.

In large diesel engines of the crosshead type used in marine and heavystationary applications, the cylinders are lubricated separately fromthe other engine components. The cylinders are lubricated on a totalloss basis with the cylinder oil being injected separately to quills oneach cylinder by means of lubricators positioned around the cylinderliner. Oil is distributed to the lubricators by means of pumps, whichare, in modern engine designs, actuated to apply the oil directly ontothe rings to reduce wastage of the oil.

One problem associated with these engines is that their manufacturerscommonly design them to use a variety of diesel fuels, ranging from goodquality high distillate fuel with low sulfur and low asphaltene contentto poorer quality intermediate or heavy fuel such as marine residualfuel with generally high sulfur and higher asphaltene content.

The high stresses encountered in these engines and the use of marineresidual fuels creates the need for lubricants with a high detergencyand neutralizing capability even though the oils are exposed to thermaland other stresses only for short periods of time. Residual fuelscommonly used in these diesel engines typically contain significantquantities of sulfur, which, in the combustion process, combine withwater to form sulfuric acid, the presence of which leads to corrosivewear. In particular, in two-stroke engines for ships, areas around thecylinder liners and piston rings can be corroded and worn by the acid.Therefore, it is important for diesel engine lubricating oils to havethe ability to resist such corrosion and wear.

Accordingly, a primary function of marine diesel cylinder lubricants isto neutralize sulfur-based acidic components of high-sulfur fuel oilcombusted in low-speed 2-stroke crosshead diesel engines. Thisneutralization is accomplished by the inclusion in the marine dieselcylinder lubricant of basic species such as metallic detergents.Unfortunately the basicity of the marine diesel cylinder lubricant canbe diminished by oxidation of the marine diesel cylinder lubricant(caused by the thermal and oxidative stress the lubricant undergoes inthe engine), thus decreasing the lubricant's neutralization ability. Theoxidation can be accelerated if the marine diesel cylinder lubricantscontain oxidation catalysts such as wear metals that are generally knownto be present in the lubricant during engine operation.

Marine two-stroke diesel cylinder lubricants must meet performancedemands in order to comply with the severe operating conditions requiredfor more modern larger bore, two-stroke cross-head diesel marine engineswhich are run at high outputs and severe loads and higher temperaturesof the cylinder liner.

Presently, the marine industry has been dealing with challenges of agrowing shortage of Group I category basestocks, typically used formarine engine oils, as well as lower sulfur fuel levels forced bylegislation. In addition to these challenges, marine two-stroke dieselcylinder lubricants must meet performance demands in order to complywith the severe operating conditions required for more modern largerbore, two-stroke cross-head diesel marine engines which are run at highoutputs and severe loads and higher temperatures of the cylinder liner.Therefore, there is a further need for marine cylinder lubricating oilcompositions which are compatible with basestocks other than Group Ibasestocks while having improved detergency and high heat stability athigh temperatures to comply with the severe load conditions of the largebore two-stroke engines operating on fuels with a wide range of sulfur.

Recently, generic design changes in large bore, low-speed, two-strokeengines as well as changes in operations (both driven by fuelefficiency) have contributed to the frequent occurrence of severe coldcorrosion. Cold corrosion is caused by sulfuric acid. The sulfur oxidesthat result from combustion of the fuel (typically a Heavy Fuel Oilwith >2 wt % sulfur) will, with the water formed during combustion andthe water from the scavenge air, form sulfuric acid. When the linertemperature drops below the dew point of sulfuric acid and water, acorrosive mixture is condensed on the liner. Cylinder lubricantbasicity, cylinder lubricant feed rate of the oil to the cylinder liner,engine make and type, engine load, inlet air humidity and fuel sulfurcontent are among the factors that can influence the amount of coldcorrosion. High alkaline lubricants are used to neutralize the sulfuricacids and avoid cold corrosion of piston rings and cylinder linersurfaces. High alkalinity lubricants (e.g., up to 100 BN by the ASTMD2896 test method) are currently being marketed to help overcome severecold corrosion.

Sulfurized, overbased phenates are known compounds which are widely usedin marine applications for their detergency properties and thermalstability. However, low molecular weight alkylphenol compounds such astetrapropenyl phenol (TPP) are often used as raw materials in themanufacture of these sulfurized, overbased phenates. The process tomanufacture overbased phenates generally results in the presence of theunreacted alkylphenol in the final reaction product and ultimately inthe finished lubricating oil composition. Recent reproductive toxicitystudies have shown that in high concentrations of unreacted alkylphenol,TPP in particular, may be endocrine disruptive materials which can causeadverse effects in male and female reproductive organs.

To reduce any potential health risks to customers and avoid potentialregulatory issues, there is a further need to reduce or eliminate theamount of unreacted TPP and its unsulfurized metal salt present inlubricating oil compositions. Therefore, it would be even more desirableto develop a marine diesel cylinder lubricating oil composition that issubstantially free of unreacted TPP and its unsulfurized metal salt.

SUMMARY OF THE INVENTION

In accordance with one embodiment of the present invention, a marinediesel cylinder engine lubricating oil composition is provided whichcomprises (a) a major amount of one or more Group II basestocks, and (b)a detergent composition comprising (i) one or more alkaline earth metalsalts of an alkyl-substituted hydroxyaromatic carboxylic acid having atotal base number (TBN) of greater than 250, and (ii) one or more highoverbased alkyl aromatic sulfonic acids or salts thereof; wherein thearomatic moiety of the alkyl aromatic sulfonic acids or salts containsno hydroxyl groups; and wherein the marine diesel cylinder lubricatingoil composition has a TBN of about 5 to about 120.

In accordance with a second embodiment of the present invention, thereis provided a method for lubricating a marine two-stroke crossheaddiesel engine with a marine diesel cylinder lubricant composition havingimproved high temperature detergency and thermal stability; wherein themethod comprises operating the engine with a marine diesel cylinderlubricating oil composition comprising (a) a major amount of one or moreGroup II basestocks, and (b) a detergent composition comprising (i) oneor more alkaline earth metal salts of an alkyl-substitutedhydroxyaromatic carboxylic acid having a TBN of greater than 250, and(ii) one or more high overbased alkyl aromatic sulfonic acids or saltsthereof; wherein the aromatic moiety of the alkyl aromatic sulfonicacids or salts thereof contains no hydroxyl groups; and wherein themarine diesel cylinder lubricating oil composition has a TBN of about 5to about 120.

A third embodiment of the present invention is directed to a use of amarine diesel cylinder lubricating oil composition in a two-strokecrosshead marine diesel engine; wherein the marine diesel cylinderlubricant composition comprises (a) a major amount of one or more GroupII basestocks, and (b) a detergent composition comprising (i) one ormore alkaline earth metal salts of an alkyl-substituted hydroxyaromaticcarboxylic acid having a TBN of greater than 250, and (ii) one or morehigh overbased alkyl aromatic sulfonic acids or salts thereof; whereinthe aromatic moiety of the alkyl aromatic sulfonic acids or saltsthereof contains no hydroxyl groups; and wherein the marine dieselcylinder lubricating oil composition has a TBN of about 5 to about 120,to provide a marine diesel cylinder lubricating oil composition havingimproved high temperature detergency and thermal stability.

The present invention is based on the surprising discovery that thecombination of one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid having a TBN ofgreater than 250, and one or more high overbased alkyl aromatic sulfonicacids or salts thereof advantageously improves the high temperaturedetergency and thermal stability of a marine diesel cylinder lubricatingoil composition containing a major amount of one or more Group IIbasestocks and used in a two-stroke crosshead marine diesel engine;wherein the marine diesel cylinder lubricant has a TBN of from about 5to about 120. In addition, the combination of the one or more alkalineearth metal salts of an alkyl-substituted hydroxyaromatic carboxylicacid having a TBN of greater than 250, and one or more high overbasedalkyl aromatic sulfonic acids or salts thereof also advantageouslyimproves the storage stability of a marine diesel cylinder lubricatingoil composition containing a major amount of one or more Group IIbasestocks, and having a TBN of from about 5 to about 120.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Definitions

The term “marine diesel cylinder lubricant” or “marine diesel cylinderlubricating oil” as used herein shall be understood to mean a lubricantused in the cylinder lubrication of a low speed or medium speedtwo-stroke crosshead marine diesel engine. The marine diesel cylinderlubricant is fed to the cylinder walls through a number of injectionpoints. Marine diesel cylinder lubricants are capable of providing afilm between the cylinder liner and the piston rings and holdingpartially burned fuel residues in suspension, to thereby promote enginecleanliness and neutralize acids formed by, for example, the combustionof sulfur compounds in the fuel.

A “marine residual fuel” refers to a material combustible in largemarine engines which has a carbon residue, as defined in InternationalOrganization for Standardization (ISO) 10370) of at least 2.5 wt. %(e.g., at least 5 wt. %, or at least 8 wt. %) (relative to the totalweight of the fuel), a viscosity at 50° C. of greater than 14.0 cSt,such as the marine residual fuels defined in the InternationalOrganization for Standardization specification ISO 8217:2005, “Petroleumproducts—Fuels (class F)—Specifications of marine fuels,” the contentsof which are incorporated herein in their entirety.

A “residual fuel” refers to a fuel meeting the specification of aresidual marine fuel as set forth in the ISO 8217:2010 internationalstandard. A “low sulfur marine fuel” refers to a fuel meeting thespecification of a residual marine fuel as set forth in the ISO8217:2010 specification that, in addition, has about 1.5 wt. % or less,or even about 0.5% wt. % or less, of sulfur, relative to the totalweight of the fuel.

A “distillate fuel” refers to a fuel meeting the specification of adistillate marine fuel as set forth in the ISO 8217:2010 internationalstandard. A “low sulfur distillate fuel” refers to a fuel meeting thespecification of a distillate marine fuel set forth in the ISO 8217:2010international standard that, in addition, has about 0.1 wt. % or less oreven about 0.005 wt. % or less, of sulfur, relative to the total weightof the fuel.

The term “bright stock”, as used by persons skilled in the art, refersto base oils that are direct products of de-asphalted petroleum vacuumresiduum or derived from de-asphalted petroleum vacuum residuum afterfurther processing such as solvent extraction and/or dewaxing. For thepurposes of this invention, it also refers to deasphalted distillatecuts of a vacuum residuum process. Bright stocks generally have akinematic viscosity at 100° C. of from 28 to 36 mm²/s. One example ofsuch a bright stock is ESSO™ Core 2500 Base Oil.

The term “Group II metal” or “alkaline earth metal” means calcium,barium, magnesium, and strontium.

The term “calcium base” refers to a calcium hydroxide, calcium oxide,calcium alkoxide and the like and mixtures thereof.

The term “lime” refers to calcium hydroxide also known as slaked lime orhydrated lime.

The term “alkylphenol” refers to a phenol group having one or more alkylsubstituents at least one of which has a sufficient number of carbonatoms to impart oil solubility to the resulting phenate additive.

The term “phenate” means a salt of a phenol.

The term “lower alkanoic acid” refers to alkanoic acids having 1 through3 carbon atoms, i.e., formic acid, acetic acid and propionic acid andmixtures thereof.

The term “polyol promoter” refers to a compound having two or morehydroxy substituents, generally the sorbitol type, for example, alkyleneglycols and also derivatives thereof and functional equivalents such aspolyol ethers and hydroxycarboxylic acids.

The term “Total Base Number” or “TBN” refers to the level of alkalinityin an oil sample, which indicates the ability of the composition tocontinue to neutralize corrosive acids, in accordance with ASTM StandardNo. D2896 or equivalent procedure. The test measures the change inelectrical conductivity, and the results are expressed as mgKOH/g (theequivalent number of milligrams of KOH needed to neutralize 1 gram of aproduct). Therefore, a high TBN reflects strongly overbased productsand, as a result, a higher base reserve for neutralizing acids.

The term “base oil” as used herein shall be understood to mean a basestock or blend of base stocks which is a lubricant component that isproduced by a single manufacturer to the same specifications(independent of feed source or manufacturer's location); that meets thesame manufacturer's specification; and that is identified by a uniqueformula, product identification number, or both.

The term “on an actives basis” refers to additive material that is notdiluent oil or solvent.

The term “isomerized olefins” refers to olefins obtained by isomerizingolefins. Generally isomerized olefins have double bonds in differentpositions than the starting olefins from which they are derived, and mayalso have different characteristics.

In one embodiment, a marine diesel cylinder lubricating oil compositionis provided which comprises (a) a major amount of one or more Group IIbasestocks, and (b) a detergent composition comprising (i) one or morealkaline earth metal salts of an alkyl-substituted hydroxyaromaticcarboxylic acid having a TBN of greater than 250, and (ii) one or morehigh overbased alkyl aromatic sulfonic acids or salts thereof; whereinthe aromatic moiety of the alkyl aromatic sulfonic acids or saltsthereof contains no hydroxyl groups; and wherein the marine dieselcylinder lubricating oil composition has a TBN of about 5 to about 120.

In general, the marine diesel cylinder lubricating oil compositions ofthis invention will have a TBN of from about 5 to about 120. In oneembodiment, the marine diesel cylinder lubricating oil compositions ofthis invention can have a TBN of from about 20 to about 100. In oneembodiment, the marine diesel cylinder lubricating oil compositions ofthis invention can have a TBN of from about 40 to about 100. In oneembodiment, the marine diesel cylinder lubricating oil compositions ofthis invention can have a TBN of from about 55 to about 80. In oneembodiment, the marine diesel cylinder lubricating oil compositions ofthis invention can have a TBN of from about 60 to about 80. In oneembodiment, the marine diesel cylinder lubricating oil compositions ofthis invention can have a TBN of from about 10 to about 40. In oneembodiment, the marine diesel cylinder lubricating oil compositions ofthis invention can have a TBN of from about 15 to about 35.

In one embodiment, the marine diesel cylinder lubricating oilcomposition of the present invention is substantially free of anunsulfurized tetrapropenyl phenol compound and its unsulfurized metalsalt, e.g., TPP and its calcium salt. The term “substantially free” asused herein means relatively low levels, if any, of the unsulfurizedtetrapropenyl phenol and its unsulfurized metal salt, e.g., less thanabout 1.5 wt. % in the marine diesel cylinder lubricating oilcomposition. In another embodiment, the term “substantially free” isless than about 1 wt. % in the marine diesel cylinder lubricating oilcomposition. In another embodiment, the term “substantially free” isless than about 0.3 wt. % in the marine diesel cylinder lubricating oilcomposition. In another embodiment, the term “substantially free” isless than about 0.1 wt. % in the marine diesel cylinder lubricating oilcomposition. In another embodiment, the term “substantially free” isfrom about 0.0001 to about 0.3 wt. % in the marine diesel cylinderlubricating oil composition.

Due to low-operating speeds and high loads in marine engines, highviscosity oils (e.g., SAE 40, 50, and 60) are typically required. Themarine diesel cylinder lubricating oil compositions of this inventioncan have a kinematic viscosity ranging from about 12.5 to about 26.1centistokes (cSt) at 100° C. In another embodiment, the lubricating oilcomposition has a viscosity of about 12.5 to about 21.9, or about 16.3to about 21.9 cSt at 100° C. The kinematic viscosity of the marinediesel cylinder lubricating oil compositions is measured by ASTM D445.

The marine diesel cylinder lubricating oil compositions of the presentinvention can be prepared by any method known to a person of ordinaryskill in the art for making marine diesel cylinder lubricating oilcompositions. The ingredients can be added in any order and in anymanner. Any suitable mixing or dispersing equipment may be used forblending, mixing or solubilizing the ingredients. The blending, mixingor solubilizing may be carried out with a blender, an agitator, adisperser, a mixer (e.g., planetary mixers and double planetary mixers),a homogenizer (e.g., a Gaulin homogenizer or Rannie homogenizer), a mill(e.g., colloid mill, ball mill or sand mill) or any other mixing ordispersing equipment known in the art.

The Group II basestocks for use herein can be any petroleum derived baseoil of lubricating viscosity as defined in API Publication 1509, 14thEdition, Addendum I, December 1998. API guidelines define a base stockas a lubricant component that may be manufactured using a variety ofdifferent processes. A Group II basestock generally refers to apetroleum derived lubricating base oil having a total sulfur contentequal to or less than 300 parts per million (ppm) (as determined by ASTMD 2622, ASTM D 4294, ASTM D 4927 or ASTM D 3120), a saturates contentequal to or greater than 90 weight percent (as determined by ASTM D2007), and a viscosity index (VI) of between 80 and 120 (as determinedby ASTM D 2270).

In one embodiment, the one or more Group II basestocks can be a blend ormixture of two or more, three or more, or even four or more Group IIbasestocks having different molecular weights and viscosities, whereinthe blend is processed in any suitable manner to create a base oilhaving suitable properties (such as the viscosity and TBN values,discussed above) for use in a marine diesel engine.

The one or more Group II basestocks for use in the marine diesel enginelubricating oil compositions of this invention are typically present ina major amount, e.g., an amount greater than about 50 wt. %, or greaterthan about 70 wt. %, based on the total weight of the composition. Inone embodiment, the one or more Group II basestocks are present in anamount of from 70 wt. % to about 95 wt. %, based on the total weight ofthe composition. In one embodiment, the one or more Group II basestocksare present in an amount of from 70 wt. % to about 85 wt. %, based onthe total weight of the composition.

If desired, the marine diesel engine lubricating oil compositions of thepresent invention can contain minor amounts of basestocks other than aGroup II basestock. For example, the marine diesel engine lubricatingoil compositions can contain minor amounts of Groups I or III-Vbasestocks as defined in API Publication 1509, 16^(th) Edition, AddendumI, October, 2009. Group IV base oils are polyalphaolefins (PAO).

As stated above, the marine diesel cylinder lubricating oil compositionsfor use in marine diesel engines typically have a kinematic viscosity inthe range of 12.5 to 26.1 cSt at 100° C. In order to formulate such alubricant, a bright stock may be combined with a low viscosity oil,e.g., an oil having a viscosity from 4 to 6 cSt at 100° C. However,supplies of bright stock are dwindling and therefore bright stock cannotbe relied upon to increase the viscosity of marine cylinder lubricantsto the desired ranges that manufacturers recommend. One solution to thisproblem is to use thickeners such as, for example, polyisobutylene (PIB)or viscosity index improver compounds such as olefin copolymers tothicken the marine diesel cylinder lubricating oil compositions. PIB isa commercially available material from several manufacturers. The PIB istypically a viscous oil-miscible liquid, having a weight averagemolecular weight in the range of about 1,000 to about 8,000, or fromabout 1,500 to about 6,000, and a viscosity in the range of about 2,000to about 5,000 or about 6,000 cSt (at 100° C.). The amount of PIB addedto the marine diesel cylinder lubricating oil compositions will normallybe from about 1 to about 20 wt. % of the finished oil, or from about 2to about 15 wt. % of the finished oil, or from about 4 to about 12 wt. %of the finished oil.

Group I base oils generally refer to a petroleum derived lubricatingbase oil having a saturates content of less than 90 wt. % (as determinedby ASTM D 2007) and/or a total sulfur content of greater than 300 ppm(as determined by ASTM D 2622, ASTM D 4294, ASTM D 4297 or ASTM D 3120)and has a viscosity index (VI) of greater than or equal to 80 and lessthan 120 (as determined by ASTM D 2270).

Group I base oils can comprise light overhead cuts and heavier side cutsfrom a vacuum distillation column and can also include, for example,Light Neutral, Medium Neutral, and Heavy Neutral base stocks. Thepetroleum derived base oil also may include residual stocks or bottomsfractions, such as, for example, bright stock. Bright stock is a highviscosity base oil which has been conventionally produced from residualstocks or bottoms and has been highly refined and dewaxed. Bright stockcan have a kinematic viscosity greater than about 180 cSt at 40° C., oreven greater than about 250 cSt at 40° C., or even ranging from about500 to about 1100 cSt at 40° C. In one embodiment, a Group I basestockcomprises ExxonMobil CORE®100, ExxonMobil CORE®150, ExxonMobil CORE®600,or ExxonMobil CORE®2500, or mixture thereof.

A Group III basestock generally has a total sulfur content less than orequal to 0.03 wt. % (as determined by ASTM D 2270), a saturates contentof greater than or equal to 90 wt. % (as determined by ASTM D 2007), anda viscosity index (VI) of greater than or equal to 120 (as determined byASTM D 4294, ASTM D 4297 or ASTM D 3120). In one embodiment, thebasestock is a Group III basestock, or a blend of two or more differentGroup III basestocks.

In general, Group III basestocks derived from petroleum oils areseverely hydrotreated mineral oils. Hydrotreating involves reactinghydrogen with the basestock to be treated to remove heteroatoms from thehydrocarbon, reduce olefins and aromatics to alkanes and cycloparaffinsrespectively, and in very severe hydrotreating, open up naphthenic ringstructures to non-cyclic normal and iso-alkanes (“paraffins”). In oneembodiment, a Group III basestock has a paraffinic carbon content (%C_(p)) of at least about 70%, as determined by test method ASTM D3238-95 (2005), “Standard Test Method for Calculation of CarbonDistribution and Structural Group Analysis of Petroleum Oils by then-d-M Method”. In another embodiment, a Group III basestock has aparaffinic carbon content (% C_(p)) of at least about 72%. In anotherembodiment, a Group III basestock has a paraffinic carbon content (%C_(p)) of at least about 75%. In another embodiment, a Group IIIbasestock has a paraffinic carbon content (% C_(p)) of at least about78%. In another embodiment, a Group III basestock has a paraffiniccarbon content (% C_(p)) of at least about 80%. In another embodiment, aGroup III basestock has a paraffinic carbon content (% C_(p)) of atleast about 85%.

In another embodiment, a Group III basestock has a naphthenic carboncontent (% C_(n)) of no more than about 25%, as determined by ASTM D3238-95 (2005). In another embodiment, a Group III basestock has anaphthenic carbon content (% C_(n)) of no more than about 20%. Inanother embodiment, a Group III basestock has a naphthenic carboncontent (% C_(n)) of no more than about 15%. In another embodiment, aGroup III basestock has a naphthenic carbon content (% C_(n)) of no morethan about 10%.

Many of the Group III basestocks are available commercially, e.g.,Chevron UCBO basestocks; Yukong Yubase basestocks; Shell XHVI®basestocks; and ExxonMobil Exxsyn® basestocks.

In one embodiment, a Group III basestock for use herein is aFischer-Tropsch derived base oil. The term “Fischer-Tropsch derived”means that the product, fraction, or feed originates from or is producedat some stage by a Fischer-Tropsch process. For example, a FischerTropsch base oil can be produced from a process in which the feed is awaxy feed recovered from a Fischer-Tropsch synthesis, see, e.g., U.S.Patent Application Publication Nos. 2004/0159582; 2005/0077208;2005/0133407; 2005/0133409; 2005/0139513; 2005/0139514; 2005/0241990;2005/0261145; 2005/0261146; 2005/0261147; 2006/0016721; 2006/0016724;2006/0076267; 2006/013210; 2006/0201851; 2006/020185, and 2006/0289337;U.S. Pat. Nos. 7,018,525 and 7,083,713 and U.S. application Ser. Nos.11/400,570; 11/535,165 and 11/613,936, each of which are incorporatedherein by reference. In general, the process involves a complete orpartial hydroisomerization dewaxing step, employing a dual-functionalcatalyst or a catalyst that can isomerize paraffins selectively.Hydroisomerization dewaxing is achieved by contacting the waxy feed witha hydroisomerization catalyst in an isomerization zone underhydroisomerizing conditions.

Fischer-Tropsch synthesis products can be obtained by well-knownprocesses such as, for example, the commercial SASOL® Slurry PhaseFischer-Tropsch technology, the commercial SHELL® Middle DistillateSynthesis (SMDS) Process, or by the non-commercial EXXON® Advanced GasConversion (AGC-21) process. Details of these processes and others aredescribed in, for example, WO-A-9934917; WO-A-9920720; WO-A-05107935;EP-A-776959; EP-A-668342; U.S. Pat. Nos. 4,943,672, 5,059,299;5,733,839; and RE39073; and U.S. Patent Application Publication No.2005/0227866. The Fischer-Tropsch synthesis product can containhydrocarbons having 1 to about 100 carbon atoms or, in some cases, morethan 100 carbon atoms, and typically includes paraffins, olefins andoxygenated products.

A Group IV basestock, or polyalphaolefin (PAO) are typically made by theoligomerization of low molecular weight alpha-olefins, e.g.,alpha-olefins containing at least 6 carbon atoms. In one embodiment, thealpha-olefins are alpha-olefins containing 10 carbon atoms. PAOs aremixtures of dimers, trimers, tetramers, etc., with the exact mixturedepending upon the viscosity of the final basestock desired. PAOs aretypically hydrogenated after oligomerization to remove any remainingunsaturation.

Group V base oils include all other base oils not included in Group I,II, III, or IV.

The marine diesel cylinder lubricating oil compositions of the presentinvention further comprise a detergent composition comprising (i) one ormore alkaline earth metal salt of an alkyl-substituted hydroxyaromaticcarboxylic acid having a TBN of greater than 250, and (ii) one or morehigh overbased alkyl aromatic sulfonic acids or salts thereof; whereinthe aromatic moiety of the alkyl aromatic sulfonic acids or saltsthereof contains no hydroxyl groups.

In general, the one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid and the one or morehigh overbased alkyl aromatic sulfonic acids or salts thereof areprovided as a concentrate in each of the additives are incorporated intoa substantially inert, normally liquid organic diluent such as, forexample, mineral oil, naphtha, benzene, toluene or xylene to form anadditive concentrate. These concentrates usually contain from about 10%to about 90% by weight of such diluent or from about 20% to about 80% byweight of such diluent, with the remaining amount being the specificadditive. Typically, a neutral oil having a viscosity of about 4 toabout 8.5 cSt at 100° C. and preferably about 4 to about 6 cSt at 100°C. will be used as the diluent, though synthetic oils, as well as otherorganic liquids which are compatible with the additives and finishedlubricating oil can also be used.

In one embodiment, the concentrate is substantially free of anunsulfurized tetrapropenyl phenol compound and its unsulfurized metalsalt, e.g., TPP and its calcium salt. The term “substantially free” asused herein means relatively low levels, if any, of the unsulfurizedtetrapropenyl phenol and its unsulfurized metal salt, e.g., less thanabout 1.5 wt. % in the concentrate. In another embodiment, the term“substantially free” is less than about 1 wt. % in the concentrate. Inanother embodiment, the term “substantially free” is less than about 0.3wt. % in the concentrate. In another embodiment, the term “substantiallyfree” is less than about 0.1 wt. % in the concentrate. In anotherembodiment, the term “substantially free” is from about 0.0001 to about0.3 wt. % in the concentrate.

The detergent composition employed in the marine diesel cylinderlubricating oil compositions of the present invention includes one ormore alkaline earth metal salts of an alkyl-substituted hydroxyaromaticcarboxylic acid having a TBN of greater than 250. The TBN of the one ormore alkaline earth metal salts of an alkyl-substituted hydroxyaromaticcarboxylic acid are on an actives basis. In one embodiment, the one ormore alkaline earth metal salts of an alkyl-substituted hydroxyaromaticcarboxylic acid have a TBN of greater than 250 and up to about 800. Inone embodiment, the one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid have a TBN of greaterthan 250 and up to about 750. In one embodiment, the one or morealkaline earth metal salts of an alkyl-substituted hydroxyaromaticcarboxylic acid have a TBN of greater than 250 and up to about 700. Inone embodiment, the one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid have a TBN of greaterthan 250 and up to about 650. In one embodiment, the one or morealkaline earth metal salts of an alkyl-substituted hydroxyaromaticcarboxylic acid have a TBN of greater than 250 and up to about 600. Inone embodiment, the one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid have a TBN of greaterthan 250 and up to about 410.

In another embodiment, the one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid have a TBN of fromabout 260 to about 800. In one embodiment, the one or more alkalineearth metal salts of an alkyl-substituted hydroxyaromatic carboxylicacid have a TBN of from about 260 to about 750. In one embodiment, theone or more alkaline earth metal salts of an alkyl-substitutedhydroxyaromatic carboxylic acid have a TBN of from about 260 to about700. In one embodiment, the one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid have a TBN of fromabout 260 to about 650. In one embodiment, the one or more alkalineearth metal salts of an alkyl-substituted hydroxyaromatic carboxylicacid have a TBN of from about 260 to about 600. In one embodiment, theone or more alkaline earth metal salts of an alkyl-substitutedhydroxyaromatic carboxylic acid have a TBN of from about 260 and up toabout 410.

In another embodiment, the one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid have a TBN of greaterthan or equal to about 300. In another embodiment, the one or morealkaline earth metal salts of an alkyl-substituted hydroxyaromaticcarboxylic acid have a TBN of from about 300 to about 800. In oneembodiment, the one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid have a TBN of fromabout 300 to about 750. In one embodiment, the one or more alkalineearth metal salts of an alkyl-substituted hydroxyaromatic carboxylicacid have a TBN of from about 300 to about 700. In one embodiment, theone or more alkaline earth metal salts of an alkyl-substitutedhydroxyaromatic carboxylic acid have a TBN of from about 300 to about650. In one embodiment, the one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid have a TBN of fromabout 300 to about 600. In one embodiment, the one or more alkalineearth metal salts of an alkyl-substituted hydroxyaromatic carboxylicacid have a TBN of from about 300 to about 410.

In one preferred embodiment, the one or more alkaline earth metal saltsof an alkyl-substituted hydroxyaromatic carboxylic acid are one or morealkaline earth metal salts of an alkyl-substituted hydroxybenzoic acidhaving a TBN of greater than 250. In one preferred embodiment, the oneor more alkaline earth metal salts of an alkyl-substitutedhydroxyaromatic carboxylic acid are calcium alkyl-substitutedhydroxyaromatic carboxylic acids having a TBN of greater than 250. Inanother preferred embodiment, the one or more alkaline earth metal saltsof an alkyl-substituted hydroxyaromatic carboxylic acid has a majoramount of one or more alkaline earth metal salts ofmono-alkyl-substituted hydroxyaromatic carboxylic acid having a TBN ofgreater than 250.

In one preferred embodiment, the one or more alkaline earth metal saltsof an alkyl-substituted hydroxyaromatic carboxylic acid are one or morealkaline earth metal salts of an alkyl-substituted hydroxybenzoic acidhaving a TBN of greater than or equal to about 300. In one preferredembodiment, the one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid are calciumalkyl-substituted hydroxyaromatic carboxylic acids having a TBN ofgreater than or equal to about 300. In another preferred embodiment, theone or more alkaline earth metal salts of an alkyl-substitutedhydroxyaromatic carboxylic acid has a major amount of one or morealkaline earth metal salts of mono-alkyl-substituted hydroxyaromaticcarboxylic acid having a TBN of greater than or equal to about 300.

Suitable hydroxyaromatic compounds include mononuclear monohydroxy andpolyhydroxy aromatic hydrocarbons having 1 to 4, and preferably 1 to 3,hydroxyl groups. Suitable hydroxyaromatic compounds include phenol,catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.The preferred hydroxyaromatic compound is phenol.

The alkyl-substituted moiety of the alkaline earth metal salt of analkyl-substituted hydroxyaromatic carboxylic acid can be derived from analpha olefin having from about 10 to about 80 carbon atoms. In oneembodiment, the alkyl-substituted moiety of the alkaline earth metalsalt of an alkyl-substituted hydroxyaromatic carboxylic acid can bederived from an alpha olefin having from about 10 to about 40 carbonatoms. In one embodiment, the alkyl-substituted moiety of the alkalineearth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acidcan be derived from an alpha olefin having from about 12 to about 28carbon atoms. The olefins employed may be linear, isomerized linear,branched or partially branched linear. The olefin may be a mixture oflinear olefins, a mixture of isomerized linear olefins, a mixture ofbranched olefins, a mixture of partially branched linear or a mixture ofany of the foregoing.

In one embodiment, the mixture of linear olefins that may be used is amixture of normal alpha olefins selected from olefins having from about12 to about 28, or about 20 to 28, carbon atoms per molecule. In oneembodiment, the normal alpha olefins are isomerized using at least oneof a solid or liquid catalyst.

In another embodiment, the olefins include one or more olefinscomprising C₉ to C₁₈ oligomers of monomers selected from propylene,butylene or mixtures thereof. Generally, the one or more olefins willcontain a major mount of the C₉ to C₁₈ oligomers of monomers selectedfrom propylene, butylene or mixtures thereof. Examples of such olefinsinclude propylene tetramer, butylene trimer and the like. As one skilledin the art will readily appreciate, other olefins may be present. Forexample, the other olefins that can be used in addition to the C₉ to C₁₈oligomers include linear olefins, cyclic olefins, branched olefins otherthan propylene oligomers such as butylene or isobutylene oligomers,arylalkylenes and the like and mixtures thereof. Suitable linear olefinsinclude 1-hexene, 1-nonene, 1-decene, 1-dodecene and the like andmixtures thereof. Especially suitable linear olefins are high molecularweight normal alpha-olefins such as C₁₆ to C₃₀ normal alpha-olefins,which can be obtained from processes such as ethylene oligomerization orwax cracking. Suitable cyclic olefins include cyclohexene, cyclopentene,cyclooctene and the like and mixtures thereof. Suitable branched olefinsinclude butylene dimer or trimer or higher molecular weight isobutyleneoligomers, and the like and mixtures thereof. Suitable arylalkylenesinclude styrene, methyl styrene, 3-phenylpropene, 2-phenyl-2-butene andthe like and mixtures thereof.

In one embodiment, the alkyl-substituted moiety of the alkaline earthmetal salt of an alkyl-substituted hydroxyaromatic carboxylic acid cancontain a mixture of C₁₂ alkyl groups and C₂₀ to C₂₈ linear olefins. Inone embodiment, the alkyl-substituted moiety of the alkaline earth metalsalt of an alkyl-substituted hydroxyaromatic carboxylic acid can containup to about 50% by weight of C₁₂ alkyl groups in mixture with at leastabout 50% by weight of C₂₀ to C₂₈ linear olefins.

In one embodiment, the alkyl-substituted moiety of the alkaline earthmetal salt of an alkyl-substituted hydroxyaromatic carboxylic acid cancontain up to 50% by weight of C₂₀ to C₂₈ linear olefins in mixture withat least 50% by weight of a branched hydrocarbyl radical derived frompropylene oligomer. In another embodiment, the alkyl-substituted moietyof the alkaline earth metal salt of an alkyl-substituted hydroxyaromaticcarboxylic acid can contain up to 85% by weight of C₂₀ to C₂₈ linearolefins in mixture with at least 15% by weight of a branched hydrocarbylradical derived from propylene oligomer.

In one embodiment, at least about 75 mole % (e.g., at least about 80mole %, at least about 85 mole %, at least about 90 mole %, at leastabout 95 mole %, or at least about 99 mole %) of the alkyl groupscontained within the alkaline earth metal salt of an alkyl-substitutedhydroxyaromatic carboxylic acid are C₂₀ alkyl groups or higher. Inanother embodiment, the alkaline earth metal salt of analkyl-substituted hydroxyaromatic carboxylic acid is an alkaline earthmetal salt of an alkyl-substituted hydroxybenzoic acid that is derivedfrom an alkyl-substituted hydroxybenzoic acid in which the alkyl groupsare the residue of normal alpha-olefins containing at least 75 mole %C₂₀ or higher normal alpha-olefins.

In another embodiment, at least about 50 mole % (e.g., at least about 60mole %, at least about 70 mole %, at least about 80 mole %, at leastabout 85 mole %, at least about 90 mole %, at least about 95 mole %, orat least about 99 mole %) of the alkyl groups contained within thealkaline earth metal salt of an alkyl-substituted hydroxyaromaticcarboxylic acid are about C₁₄ to about C₁₈.

The resulting alkaline earth metal salt of an alkyl-substitutedhydroxyaromatic carboxylic acid having a TBN of greater than 250 can bea mixture of ortho and para isomers. In one embodiment, the product willcontain about 1 to 99% ortho isomer and 99 to 1% para isomer. In anotherembodiment, the product will contain about 5 to 70% ortho and 95 to 30%para isomer.

The alkaline earth metal salts of an alkyl-substituted hydroxyaromaticcarboxylic acid are one in which the BN of the alkaline earth metalsalts of an alkyl-substituted hydroxyaromatic carboxylic acid has beenincreased by a process such as the addition of a base source (e.g.,lime) and an acidic overbasing compound (e.g., carbon dioxide). Methodsfor overbasing are within the purview of one skilled in the art.

Generally, the amount of the one or more alkaline earth metal salts ofan alkyl-substituted hydroxyaromatic carboxylic acid having a TBN ofgreater than 250 present in a marine diesel cylinder lubricating oilcomposition having a TBN of about 5 to about 120 can range from about0.1 wt. % to about 35 wt. % on an actives basis, based on the totalweight of the marine diesel cylinder lubricating oil composition. In oneembodiment, the amount of the one or more alkaline earth metal salts ofan alkyl-substituted hydroxyaromatic carboxylic acid having a TBN ofgreater than 250 present in the marine diesel cylinder lubricating oilcomposition a marine diesel cylinder lubricating oil composition havinga TBN of about 20 to about 100 can range from about 1 wt. % to about 25wt. % on an actives basis, based on the total weight of the marinediesel cylinder lubricating oil composition. In one embodiment, theamount of the one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid having a TBN ofgreater than 250 present in the marine diesel cylinder lubricating oilcomposition a also marine diesel cylinder lubricating oil compositionhaving a TBN of about 20 to about 60 can range from about 3 wt. % toabout 20 wt. % on an actives basis, based on the total weight of themarine diesel cylinder lubricating oil composition. In one embodiment,the amount of the one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid having a TBN ofgreater than 250 present in the marine diesel cylinder lubricating oilcomposition a marine diesel cylinder lubricating oil composition havinga TBN of about 30 to about 50 can range from about 3 wt. % to about 15wt. % on an actives basis, based on the total weight of the marinediesel cylinder lubricating oil composition.

The detergent composition employed in the marine diesel cylinderlubricating oil compositions of the present invention also includes oneor more high overbased alkyl aromatic sulfonic acids or salts thereof.The alkyl aromatic sulfonic acids or salts thereof include alkylaromatic sulfonic acids or salts thereof obtained by the alkylation ofan aromatic compound. The alkyl aromatic compound is then sulfonated toform an alkyl aromatic sulfonic acid. If desired, the alkyl aromaticsulfonic acid can be neutralized with caustic to obtain an alkali oralkaline earth metal alkyl aromatic sulfonate compound.

At least one aromatic compound or a mixture of aromatic compounds may beused to form the alkyl aromatic sulfonic acid or salt thereof. Suitablearomatic compounds or the aromatic compound mixture comprise at leastone of monocyclic aromatics, such as benzene, toluene, xylene, cumene ormixtures thereof. In one preferred embodiment the at least one aromaticmoiety of the alkyl aromatic sulfonic acids or salts contains nohydroxyl groups. In one preferred embodiment, the at least one aromaticmoiety of the alkyl aromatic sulfonic acids or salts compound is not aphenol. In one embodiment, the at least one aromatic compound oraromatic compound mixture is toluene.

The at least one alkyl aromatic compound or the mixture of aromaticcompounds is commercially available or may be prepared by methods thatare well known in the art.

The alkylating agent employed to alkylate the aromatic compound may bederived from a variety of sources. Such sources include the normal alphaolefins, linear alpha olefins, isomerized linear alpha olefins,dimerized and oligomerized olefins, and olefins derived from olefinmetathesis. The olefin may be a single carbon number olefin, or it maybe a mixture of linear olefins, a mixture of isomerized linear olefins,a mixture of branched olefins, a mixture of partially branched olefins,or a mixture of any of the foregoing. Another source from which theolefins may be derived is through cracking of petroleum orFischer-Tropsch wax. The Fischer-Tropsch wax may be hydrotreated priorto cracking. Other commercial sources include olefins derived fromparaffin dehydrogenation and oligomerization of ethylene and otherolefins, methanol-to-olefin processes (methanol cracker) and the like.

The olefins may selected from olefins with carbon numbers ranging fromabout 8 carbon atoms to about 60 carbon atoms. In one embodiment, theolefins are selected from olefins with carbon numbers ranging from about10 to about 50 carbon atoms. In one embodiment, the olefins are selectedfrom olefins with carbon numbers ranging from about 12 to about 40carbon atoms.

In another embodiment, the olefin or the mixture of olefins is selectedfrom linear alpha olefins or isomerized alpha olefins containing fromabout 8 to about 60 carbon atoms. In one embodiment, the mixture ofolefins is selected from linear alpha olefins or isomerized alphaolefins containing from about 10 to about 50 carbon atoms. In oneembodiment, the mixture of olefins is selected from linear alpha olefinsor isomerized olefins containing from about 12 to about 40 carbon atoms.

The linear olefins that may be used for the alkylation reaction may beone or a mixture of normal alpha olefins selected from olefins havingfrom about 8 to about 60 carbon atoms per molecule. In one embodiment,the normal alpha olefin is selected from olefins having from about 10 toabout 50 carbon atoms per molecule. In one embodiment, the normal alphaolefin is selected from olefins having from about 12 to about 40 carbonatoms per molecule.

In one embodiment, the mixture of branched olefins is selected frompolyolefins which may be derived from C₃ or higher monoolefins (e.g.,propylene oligomers, butylenes oligomers, or co-oligomers etc.). In oneembodiment, the mixture of branched olefins is either propyleneoligomers or butylenes oligomers or mixtures thereof.

In one embodiment, the aromatic compound is alkylated with a mixture ofnormal alpha olefins containing from C₈ to C₆₀ carbon atoms. In oneembodiment, the aromatic compound is alkylated with a mixture of normalalpha olefins containing from C₁₀ to C₅₀ carbon atoms. In anotherembodiment, the aromatic compound is alkylated with a mixture of normalalpha olefins containing from C₁₂ to C₄₀ carbon atoms to yield anaromatic alkylate.

The normal alpha olefins employed to make the alkylaromatic sulfonicacid or salt thereof are commercially available or may be prepared bymethods that are well known in the art.

In one embodiment, the normal alpha olefins are isomerized using a solidor a liquid acid catalyst. A solid catalyst preferably has at least onemetal oxide and an average pore size of less than 5.5 angstroms. In oneembodiment, the solid catalyst is a molecular sieve with aone-dimensional pore system, such as SM-3, MAPO-11, SAPO-11, SSZ-32,ZSM-23, MAPO-39, SAPO-39, ZSM-22 or SSZ-20. Other possible acidic solidcatalysts useful for isomerization include ZSM-35, SUZ-4, NU-23, NU-87and natural or synthetic ferrierites. These molecular sieves are wellknown in the art and are discussed in Rosemarie Szostak's Handbook ofMolecular Sieves (New York, Van Nostrand Reinhold, 1992) which is hereinincorporated by reference for all purposes. A liquid type ofisomerization catalyst that can be used is iron pentacarbonyl (Fe(CO)₅).

The process for isomerization of normal alpha olefins may be carried outin batch or continuous mode. The process temperatures may range fromabout 50° C. to about 250° C. In the batch mode, a typical method usedis a stirred autoclave or glass flask, which may be heated to thedesired reaction temperature. A continuous process is most efficientlycarried out in a fixed bed process. Space rates in a fixed bed processcan range from about 0.1 to about 10 or more weight hourly spacevelocity.

In a fixed bed process, the isomerization catalyst is charged to thereactor and activated or dried at a temperature of at least 125° C.under vacuum or flowing inert, dry gas. After activation, thetemperature of the isomerization catalyst is adjusted to the desiredreaction temperature and a flow of the olefin is introduced into thereactor. The reactor effluent containing the partially-branched,isomerized olefins is collected. The resulting partially-branched,isomerized olefins contain a different olefin distribution (i.e., alphaolefin, beta olefin; internal olefin, tri-substituted olefin, andvinylidene olefin) and branching content than that of the unisomerizedolefin and conditions are selected in order to obtain the desired olefindistribution and the degree of branching.

Typically, the alkylated aromatic compound may be prepared using aBronsted acid catalyst, a Lewis acid catalyst, or solid acidiccatalysts.

The Bronsted acid catalyst may be selected from a group comprisinghydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid,perchloric acid, trifluoromethane sulfonic acid, fluorosulfonic acid,and nitric acid and the like. In one embodiment, the Bronsted acidcatalyst is hydrofluoric acid.

The Lewis acid catalyst may be selected from the group of Lewis acidscomprising aluminum trichloride, aluminum tribromide, aluminumtriiodide, boron trifluoride, boron tribromide, boron triiodide and thelike. In one embodiment, the Lewis acid catalyst is aluminumtrichloride.

The solid acidic catalysts may be selected from a group comprisingzeolites, acid clays, and/or silica-alumina. An eligible solid catalystis a cation exchange resin in its acid form, for example, crosslinkedsulfonic acid catalyst. The catalyst may be a molecular sieve. Suitablemolecular sieves are silica-aluminophosphate molecular sieves or metalsilica-aluminophosphate molecular sieves, in which the metal may be, forexample, iron, cobalt or nickel. Other suitable examples of solid acidiccatalysts are disclosed in U.S. Pat. No. 7,183,452, the contents ofwhich are incorporated by reference herein.

The Bronsted acid catalyst may be regenerated after it becomesdeactivated (i.e., the catalyst has lost all or some portion of itscatalytic activity). Methods that are well known in the art may be usedto regenerate the acid catalyst, for example, hydrofluoric acid.

The alkylation technologies used to produce the alkyl aromatic willinclude Bronsted and/or Lewis acids as well as solid acid catalystsutilized in a batch, semi-batch or continuous process operating atbetween from about 0 to about 300° C.

The acid catalyst may be recycled when used in a continuous process. Theacid catalyst may be recycled or regenerated when used in a batchprocess or a continuous process.

In one embodiment, the alkylation process is carried out by reacting afirst amount of at least one aromatic compound or a mixture of aromaticcompounds with a first amount of a mixture of olefin compounds in thepresence of a Bronsted acid catalyst, such as hydrofluoric acid, in afirst reactor in which agitation is maintained, thereby producing afirst reaction mixture. The resulting first reaction mixture is held ina first alkylation zone under alkylation conditions for a timesufficient to convert the olefin to aromatic alkylate (i.e., a firstreaction product). After a desired time, the first reaction product isremoved from the alkylation zone and fed to a second reactor wherein thefirst reaction product is reacted with an additional amount of at leastone aromatic compound or a mixture of aromatic compounds and anadditional amount of acid catalyst and, optionally, with an additionalamount of a mixture of olefin compounds wherein agitation is maintained.A second reaction mixture results and is held in a second alkylationzone under alkylation conditions for a time sufficient to convert theolefin to aromatic alkylate (i.e., a second reaction product). Thesecond reaction product is fed to a liquid-liquid separator to allowhydrocarbon (i.e., organic) products to separate from the acid catalyst.The acid catalyst may be recycled to the reactor(s) in a closed loopcycle. The hydrocarbon product is further treated to remove excessun-reacted aromatic compounds and, optionally, olefinic compounds fromthe desired alkylate product. The excess aromatic compounds may also berecycled to the reactor(s).

In another embodiment, the reaction takes place in more than tworeactors which are located in series. Instead of feeding the secondreaction product to a liquid-liquid separator, the second reactionproduct is fed to a third reactor wherein the second reaction product isreacted with an additional amount of at least one aromatic compound or amixture of aromatic compounds and an additional amount of acid catalystand, optionally, with an additional amount of a mixture of olefincompounds wherein agitation is maintained. A third reaction mixtureresults and is held in a third alkylation zone under alkylationconditions for a time sufficient to convert the olefin to aromaticalkylate (i.e., a third reaction product). The reactions take place inas many reactors as necessary to obtain the desired alkylated aromaticreaction product.

The total charge mole ratio of Bronsted acid catalyst to the olefincompounds is about 0.1 to about 1 for the combined reactors. In oneembodiment, the charge mole ratio of Bronsted acid catalyst to theolefin compounds is no more than about 0.7 to about 1 in the firstreactor and no less than about 0.3 to about 1 in the second reactor.

The total charge mole ratio of the aromatic compound to the olefincompounds is about 7.5:1 to about 1:1 for the combined reactors. In oneembodiment, the charge mole ratio of the aromatic compound to the olefincompounds is no less than about 1.4:1 to about 1:1 in the first reactorand is no more than about 6.1:1 to about 1:1 in the second reactor.

Many types of reactor configurations may be used for the reactor zone.These include, but are not limited to, batch and continuous stirred tankreactors, reactor riser configurations, ebulating bed reactors, andother reactor configurations that are well known in the art. Many suchreactors are known to those skilled in the art and are suitable for thealkylation reaction. Agitation is critical for the alkylation reactionand can be provided by rotating impellers, with or without baffles,static mixers, kinetic mixing in risers, or any other agitation devicesthat are well known in the art. The alkylation process may be carriedout at temperatures from about 0° C. to about 100° C. The process iscarried out under sufficient pressure that a substantial portion of thefeed components remain in the liquid phase. Typically, a pressure of 0to 150 psig is satisfactory to maintain feed and products in the liquidphase.

The residence time in the reactor is a time that is sufficient toconvert a substantial portion of the olefin to alkylate product. Thetime required is from about 30 seconds to about 30 minutes. A moreprecise residence time may be determined by those skilled in the artusing batch stirred tank reactors to measure the kinetics of thealkylation process.

The at least one aromatic compound or mixture of aromatic compounds andthe olefin compounds may be injected separately into the reaction zoneor may be mixed prior to injection. Both single and multiple reactionzones may be used with the injection of the aromatic compounds and theolefin compounds into one, several, or all reaction zones. The reactionzones need not be maintained at the same process conditions. Thehydrocarbon feed for the alkylation process may comprise a mixture ofaromatic compounds and olefin compounds in which the molar ratio ofaromatic compounds to olefins is from about 0.5:1 to about 50:1 or more.In the case where the molar ratio of aromatic compounds to olefinis >1.0 to 1, there is an excess amount of aromatic compounds present.In one embodiment, an excess of aromatic compounds is used to increasereaction rate and improve product selectivity. When excess aromaticcompounds are used, the excess un-reacted aromatic in the reactoreffluent can be separated, e.g., by distillation, and recycled to thereactor.

Once the alkyl aromatic product is obtained as described above, it isfurther reacted to form an alkyl aromatic sulfonic acid, and can then beneutralized to the corresponding sulfonate. Sulfonation of the alkylaromatic compound may be performed by any method known to one ofordinary skill in the art. The sulfonation reaction is typically carriedout in a continuous falling film tubular reactor maintained at about 45°C. to about 75° C. For example, the alkyl aromatic compound is placed inthe reactor along with sulfur trioxide diluted with air therebyproducing an alkylaryl sulfonic acid. Other sulfonation reagents, suchas sulfuric acid, chlorosulfonic acid or sulfamic acid may also beemployed. In one embodiment, the alkyl aromatic compound is sulfonatedwith sulfur trioxide diluted with air. The charge mole ratio of sulfurtrioxide to alkylate is maintained at about 0.8 to about 1.1:1.

If desired, neutralization of the alkyl aromatic sulfonic acid may becarried out in a continuous or batch process by any method known to aperson skilled in the art to produce alkyl aromatic sulfonates.Typically, an alkyl aromatic sulfonic acid is neutralized with a sourceof alkali or alkaline earth metal or ammonia, thereby producing an alkylaromatic sulfonate. Non-limiting examples of suitable alkali metalsinclude lithium, sodium, potassium, rubidium, and cesium. In oneembodiment, a suitable alkali metal includes sodium and potassium. Inanother embodiment, a suitable alkali metal is sodium. Non-limitingexamples of suitable alkaline earth metals include calcium, barium,magnesium, or strontium and the like. In one embodiment, a suitablealkaline earth metal is calcium. In one embodiment, the source is analkali metal base such as an alkali metal hydroxide, e.g., sodiumhydroxide or potassium hydroxide. In one embodiment, the source is analkaline earth metal base such as an alkaline earth metal hydroxide,e.g., calcium hydroxide.

The one or more alkyl aromatic sulfonic acid or salts thereof are one ormore high overbased alkyl aromatic sulfonic acid or salts thereof. Asdiscussed above, overbasing is one in which the TBN of the alkylaromatic sulfonic acid or salts thereof has been increased by a processsuch as, for example, the addition of a base source (e.g., lime) and anacidic overbasing compound (e.g., carbon dioxide). Methods foroverbasing are well known in the art.

In one embodiment, the one or more high overbased alkyl aromaticsulfonic acids or salts thereof will have a TBN greater than 250. In oneembodiment, the one or more high overbased alkyl aromatic sulfonic acidsor salts thereof will have a TBN of about 250 to about 700. In oneembodiment, the one or more high overbased alkyl aromatic sulfonic acidsor salts thereof will have a TBN greater than or equal to about 300. Inone embodiment, the one or more high overbased alkyl aromatic sulfonicacids or salts thereof will have a TBN of about 300 to about 700.

Generally, the amount of the one or more high overbased alkyl aromaticsulfonic acids or salts thereof present in a marine diesel cylinderlubricating oil composition having a TBN of about 5 to about 120 canrange from about 0.1 wt. % to about 34 wt. % on an actives basis, basedon the total weight of the marine diesel cylinder lubricating oilcomposition. In one embodiment, the amount of the one or more highoverbased alkyl aromatic sulfonic acids or salts thereof present in amarine diesel cylinder lubricating oil composition having a TBN of about20 to about 100 can range from about 1 wt. % to about 30 wt. % on anactives basis, based on the total weight of the marine diesel cylinderlubricating oil composition. In one embodiment, the amount of the one ormore high overbased alkyl aromatic sulfonic acids or salts thereofpresent in a marine diesel cylinder lubricating oil composition having aTBN of about 20 to about 60 can range from about 2 wt. % to about 24 wt.% on an actives basis, based on the total weight of the marine dieselcylinder lubricating oil composition. In one embodiment, the amount ofthe one or more high overbased alkyl aromatic sulfonic acids or saltsthereof present in a marine diesel cylinder lubricating oil compositionhaving a TBN of about 30 to about 50 can range from about 5 wt. % toabout 16 wt. % on an actives basis, based on the total weight of themarine diesel cylinder lubricating oil composition.

The marine diesel cylinder lubricating oil compositions of the presentinvention may also contain conventional marine diesel cylinderlubricating oil composition additives, other than the foregoing one ormore alkaline earth metal salts of an alkyl-substituted hydroxyaromaticcarboxylic acid having a TBN of greater than 250 and the one or morehigh overbased alkyl aromatic sulfonic acids or salts thereof, forimparting auxiliary functions to give a marine diesel cylinderlubricating oil composition in which these additives are dispersed ordissolved. For example, the marine diesel cylinder lubricating oilcompositions can be blended with antioxidants, ashless dispersants,other detergents, anti-wear agents, rust inhibitors, dehazing agents,demulsifying agents, metal deactivating agents, friction modifiers, pourpoint depressants, antifoaming agents, co-solvents,corrosion-inhibitors, dyes, extreme pressure agents and the like andmixtures thereof. A variety of the additives are known and commerciallyavailable. These additives, or their analogous compounds, can beemployed for the preparation of the marine diesel cylinder lubricatingoil compositions of the invention by the usual blending procedures.

In one embodiment, the marine diesel cylinder lubricating oilcompositions of the present invention contain essentially no thickener(i.e., a viscosity index improver).

Examples of antioxidants include, but are not limited to, aminic types,e.g., diphenylamine, phenyl-alpha-napthyl-amine, N,N-di(alkylphenyl)amines; and alkylated phenylene-diamines; phenolics such as, forexample, BHT, sterically hindered alkyl phenols such as2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol and2,6-di-tert-butyl-4-(2-octyl-3-propanoic) phenol; and mixtures thereof.

The ashless dispersant compounds employed in the marine diesel cylinderlubricating oil compositions of the present invention are generally usedto maintain in suspension insoluble materials resulting from oxidationduring use, thus preventing sludge flocculation and precipitation ordeposition on metal parts. Dispersants may also function to reducechanges in lubricating oil viscosity by preventing the growth of largecontaminant particles in the lubricant. The dispersant employed in thepresent invention may be any suitable ashless dispersant or mixture ofmultiple ashless dispersants for use in a marine diesel cylinderlubricating oil composition. An ashless dispersant generally comprisesan oil soluble polymeric hydrocarbon backbone having functional groupsthat are capable of associating with particles to be dispersed.

In one embodiment, an ashless dispersant is one or more basicnitrogen-containing ashless dispersants. Nitrogen-containing basicashless (metal-free) dispersants contribute to the base number or BN (ascan be measured by ASTM D 2896) of a lubricating oil composition towhich they are added, without introducing additional sulfated ash. Basicnitrogen-containing ashless dispersants useful in this invention includehydrocarbyl succinimides; hydrocarbyl succinamides; mixed ester/amidesof hydrocarbyl-substituted succinic acids formed by reacting ahydrocarbyl-substituted succinic acylating agent stepwise or with amixture of alcohols and amines, and/or with amino alcohols; Mannichcondensation products of hydrocarbyl-substituted phenols, formaldehydeand polyamines; and amine dispersants formed by reacting high molecularweight aliphatic or alicyclic halides with amines, such as polyalkylenepolyamines. Mixtures of such dispersants can also be used.

Representative examples of ashless dispersants include, but are notlimited to, amines, alcohols, amides, or ester polar moieties attachedto the polymer backbones via bridging groups. An ashless dispersant ofthe present invention may be, for example, selected from oil solublesalts, esters, amino-esters, amides, imides, and oxazolines of longchain hydrocarbon substituted mono and dicarboxylic acids or theiranhydrides; thiocarboxylate derivatives of long chain hydrocarbons, longchain aliphatic hydrocarbons having a polyamine attached directlythereto; and Mannich condensation products formed by condensing a longchain substituted phenol with formaldehyde and polyalkylene polyamine.

Carboxylic dispersants are reaction products of carboxylic acylatingagents (acids, anhydrides, esters, etc.) comprising at least about 34and preferably at least about 54 carbon atoms with nitrogen containingcompounds (such as amines), organic hydroxy compounds (such as aliphaticcompounds including monohydric and polyhydric alcohols, or aromaticcompounds including phenols and naphthols), and/or basic inorganicmaterials. These reaction products include imides, amides, and esters.

Succinimide dispersants are a type of carboxylic dispersant. They areproduced by reacting hydrocarbyl-substituted succinic acylating agentwith organic hydroxy compounds, or with amines comprising at least onehydrogen atom attached to a nitrogen atom, or with a mixture of thehydroxy compounds and amines. The term “succinic acylating agent” refersto a hydrocarbon-substituted succinic acid or a succinic acid-producingcompound, the latter encompasses the acid itself. Such materialstypically include hydrocarbyl-substituted succinic acids, anhydrides,esters (including half esters) and halides.

Succinic-based dispersants have a wide variety of chemical structures.One class of succinic-based dispersants may be represented by theformula:

wherein each R¹ is independently a hydrocarbyl group, such as apolyolefin-derived group. Typically the hydrocarbyl group is an alkylgroup, such as a polyisobutyl group. Alternatively expressed, the R¹groups can contain about 40 to about 500 carbon atoms, and these atomsmay be present in aliphatic forms. R² is an alkylene group, commonly anethylene (C₂H4) group. Examples of succinimide dispersants include thosedescribed in, for example, U.S. Pat. Nos. 3,172,892, 4,234,435 and6,165,235.

The polyalkenes from which the substituent groups are derived aretypically homopolymers and interpolymers of polymerizable olefinmonomers of 2 to about 16 carbon atoms, and usually 2 to 6 carbon atoms.The amines which are reacted with the succinic acylating agents to formthe carboxylic dispersant composition can be monoamines or polyamines.

Succinimide dispersants are referred to as such since they normallycontain nitrogen largely in the form of imide functionality, althoughthe amide functionality may be in the form of amine salts, amides,imidazolines as well as mixtures thereof. To prepare a succinimidedispersant, one or more succinic acid-producing compounds and one ormore amines are heated and typically water is removed, optionally in thepresence of a substantially inert organic liquid solvent/diluent. Thereaction temperature can range from about 80° C. up to the decompositiontemperature of the mixture or the product, which typically falls betweenabout 100° C. to about 300° C. Additional details and examples ofprocedures for preparing the succinimide dispersants of the presentinvention include those described in, for example, U.S. Pat. Nos.3,172,892, 3,219,666, 3,272,746, 4,234,435, 6,165,235 and 6,440,905.

Suitable ashless dispersants may also include amine dispersants, whichare reaction products of relatively high molecular weight aliphatichalides and amines, preferably polyalkylene polyamines. Examples of suchamine dispersants include those described in, for example, U.S. Pat.Nos. 3,275,554, 3,438,757, 3,454,555 and 3,565,804.

Suitable ashless dispersants may further include “Mannich dispersants,”which are reaction products of alkyl phenols in which the alkyl groupcontains at least about 30 carbon atoms with aldehydes (especiallyformaldehyde) and amines (especially polyalkylene polyamines). Examplesof such dispersants include those described in, for example, U.S. Pat.Nos. 3,036,003, 3,586,629, 3,591,598 and 3,980,569.

Suitable ashless dispersants may also be post-treated ashlessdispersants such as post-treated succinimides, e.g., post-treatmentprocesses involving borate or ethylene carbonate as disclosed in, forexample, U.S. Pat. Nos. 4,612,132 and 4,746,446; and the like as well asother post-treatment processes. The carbonate-treated alkenylsuccinimide is a polybutene succinimide derived from polybutenes havinga molecular weight of about 450 to about 3000, preferably from about 900to about 2500, more preferably from about 1300 to about 2400, and mostpreferably from about 2000 to about 2400, as well as mixtures of thesemolecular weights. Preferably, it is prepared by reacting, underreactive conditions, a mixture of a polybutene succinic acid derivative,an unsaturated acidic reagent copolymer of an unsaturated acidic reagentand an olefin, and a polyamine, such as disclosed in U.S. Pat. No.5,716,912, the contents of which are incorporated herein by reference.

Metal-containing or ash-forming detergents function as both detergentsto reduce or remove deposits and as acid neutralizers or rustinhibitors, thereby reducing wear and corrosion and extending enginelife. Detergents generally comprise a polar head with a long hydrophobictail. The polar head comprises a metal salt of an acidic organiccompound. The salts may contain a substantially stoichiometric amount ofthe metal in which case they are usually described as normal or neutralsalts, and would typically have a total base number or TBN (as can bemeasured by ASTM D2896) of from 0 to about 80. A large amount of a metalbase may be incorporated by reacting excess metal compound (e.g., anoxide or hydroxide) with an acidic gas (e.g., carbon dioxide). Theresulting overbased detergent comprises neutralized detergent as theouter layer of a metal base (e.g., carbonate) micelle. Such overbaseddetergents may have a TBN of about 50 or greater, or a TBN of about 100or greater, or a TBN of about 200 or greater, or a TBN of from about 250to about 450 or more.

Representative examples of other metal detergents that can be includedin the marine diesel cylinder lubricating oil composition of the presentinvention include phenates, aliphatic sulfonates, alkaline earth metalsalts of an alkyl-substituted hydroxyaromatic carboxylic acid having aTBN of equal to or less than 250, alkali metal salts of analkyl-substituted hydroxyaromatic carboxylic acid, phosphonates, andphosphinates. The salts of the alkyl-substituted hydroxyaromaticcarboxylic acid can be as described above.

Commercial products are generally referred to as neutral or overbased.Overbased metal detergents are generally produced by carbonating amixture of hydrocarbons, detergent acid, for example: sulfonic acid,carboxylate etc., metal oxide or hydroxides (for example calcium oxideor calcium hydroxide) and promoters such as xylene, methanol and water.For example, for preparing an overbased calcium sulfonate, incarbonation, the calcium oxide or hydroxide reacts with the gaseouscarbon dioxide to form calcium carbonate. The sulfonic acid isneutralized with an excess of CaO or Ca(OH)₂, to form the sulfonate.

Overbased detergents may be low overbased, e.g., an overbased salthaving a BN below about 100. In one embodiment, the BN of a lowoverbased salt may be from about 5 to about 50. In another embodiment,the BN of a low overbased salt may be from about 10 to about 30. In yetanother embodiment, the BN of a low overbased salt may be from about 15to about 20.

Overbased detergents may be medium overbased, e.g., an overbased salthaving a BN from about 100 to about 250. In one embodiment, the BN of amedium overbased salt may be from about 100 to about 200. In anotherembodiment, the BN of a medium overbased salt may be from about 125 toabout 175.

Overbased detergents may be high overbased, e.g., an overbased salthaving a BN above 250. In one embodiment, the BN of a high overbasedsalt may be from about 250 to about 550.

Examples of rust inhibitors include, but are not limited to, nonionicpolyoxyalkylene agents, e.g., polyoxyethylene lauryl ether,polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether,polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether,polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate,polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate;stearic acid and other fatty acids; dicarboxylic acids; metal soaps;fatty acid amine salts; metal salts of heavy sulfonic acid; partialcarboxylic acid ester of polyhydric alcohol; phosphoric esters;(short-chain) alkenyl succinic acids; partial esters thereof andnitrogen-containing derivatives thereof; synthetic alkarylsulfonates,e.g., metal dinonylnaphthalene sulfonates; and the like and mixturesthereof.

Examples of friction modifiers include, but are not limited to,alkoxylated fatty amines; borated fatty epoxides; fatty phosphites,fatty epoxides, fatty amines, borated alkoxylated fatty amines, metalsalts of fatty acids, fatty acid amides, glycerol esters, boratedglycerol esters; and fatty imidazolines as disclosed in U.S. Pat. No.6,372,696, the contents of which are incorporated by reference herein;friction modifiers obtained from a reaction product of a C₄ to C₇₅,preferably a C₆ to C₂₄, and most preferably a C₆ to C₂₀, fatty acidester and a nitrogen-containing compound selected from the groupconsisting of ammonia, and an alkanolamine, e.g., a mono- ordialkanolamine, and the like and mixtures thereof.

Examples of antiwear agents include, but are not limited to, zincdialkyldithiophosphates and zinc diaryldithiophosphates, e.g., thosedescribed in an article by Born et al. entitled “Relationship betweenChemical Structure and Effectiveness of Some Metallic Dialkyl- andDiaryl-dithiophosphates in Different Lubricated Mechanisms”, appearingin Lubrication Science 4-2 Jan. 1992, see for example pages 97-100; arylphosphates and phosphites, sulfur-containing esters, phosphosulfurcompounds, metal or ash-free dithiocarbamates, xanthates, alkyl sulfidesand the like and mixtures thereof.

Examples of antifoaming agents include, but are not limited to, polymersof alkyl methacrylate; polymers of dimethylsilicone and the like andmixtures thereof.

Examples of a pour point depressant include, but are not limited to,polymethacrylates, alkyl acrylate polymers, alkyl methacrylate polymers,di(tetra-paraffin phenol)phthalate, condensates of tetra-paraffinphenol, condensates of a chlorinated paraffin with naphthalene andcombinations thereof. In one embodiment, a pour point depressantcomprises an ethylene-vinyl acetate copolymer, a condensate ofchlorinated paraffin and phenol, polyalkyl styrene and the like andcombinations thereof. The amount of the pour point depressant may varyfrom about 0.01 wt. % to about 10 wt. %.

Examples of a demulsifier include, but are not limited to, anionicsurfactants (e.g., alkyl-naphthalene sulfonates, alkyl benzenesulfonates and the like), nonionic alkoxylated alkylphenol resins,polymers of alkylene oxides (e.g., polyethylene oxide, polypropyleneoxide, block copolymers of ethylene oxide, propylene oxide and thelike), esters of oil soluble acids, polyoxyethylene sorbitan ester andthe like and combinations thereof. The amount of the demulsifier mayvary from about 0.01 wt. % to about 10 wt. % a.

Examples of a corrosion inhibitor include, but are not limited to, halfesters or amides of dodecylsuccinic acid, phosphate esters,thiophosphates, alkyl imidazolines, sarcosines and the like andcombinations thereof. The amount of the corrosion inhibitor may varyfrom about 0.01 wt. % to about 0.5 wt. %.

Examples of an extreme pressure agent include, but are not limited to,sulfurized animal or vegetable fats or oils, sulfurized animal orvegetable fatty acid esters, fully or partially esterified esters oftrivalent or pentavalent acids of phosphorus, sulfurized olefins,dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurizeddicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acidesters and monounsaturated olefins, co-sulfurized blends of fatty acid,fatty acid ester and alpha-olefin, functionally-substituteddihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, epithiocompounds, sulfur-containing acetal derivatives, co-sulfurized blends ofterpene and acyclic olefins, and polysulfide olefin products, aminesalts of phosphoric acid esters or thiophosphoric acid esters and thelike and combinations thereof. The amount of the extreme pressure agentmay vary from about 0.01 wt. % to about 5 wt. %.

Each of the foregoing additives, when used, is used at a functionallyeffective amount to impart the desired properties to the lubricant.Thus, for example, if an additive is a friction modifier, a functionallyeffective amount of this friction modifier would be an amount sufficientto impart the desired friction modifying characteristics to thelubricant. Generally, the concentration of each of these additives, whenused, ranges from about 0.001% to about 20% by weight, and in oneembodiment about 0.01% to about 10% by weight based on the total weightof the lubricating oil composition.

In addition, the foregoing marine diesel cylinder lubricating oilcomposition additives may be provided as an additive package orconcentrate in which the additives are incorporated into a substantiallyinert, normally liquid organic diluent as described above. The additivepackage will typically contain one or more of the various additives,referred to above, in the desired amounts and ratios to facilitatedirect combination with the requisite amount of the oil of lubricatingviscosity.

In one embodiment, the marine diesel cylinder lubricating oilcomposition of the present invention is substantially free or free ofany dispersants and/or zinc compounds, e.g., zinc dithiophosphates. Theterm “substantially free” as used herein means relatively low levels, ifany, of each of the dispersants and/or zinc compounds, e.g., less thanabout 0.5 wt. % of each of the dispersants and/or zinc compounds in themarine diesel cylinder lubricating oil composition. In anotherembodiment, the term “substantially free” is less than about 0.1 wt. %of each of the dispersants and/or zinc compounds in the marine dieselcylinder lubricating oil composition. In another embodiment, the term“substantially free” is less than about 0.01 wt. % of each of thedispersants and/or zinc compounds in the marine diesel cylinderlubricating oil composition.

The concentration of total TPP and its unsulfurized metal salt in themarine diesel cylinder lubricating oil composition of the presentinvention (i.e., “total TPP” or “total residual TPP”) as disclosedherein and exemplified below, as well as lubricants and oil additivescontaining salts of a sulfurized alkyl-substituted hydroxyaromaticcomposition is determined by reverse phase High Performance LiquidChromatography (HPLC). In the HPLC method, samples were prepared foranalysis by weighing accurately 80 to 120 mg of sample into a 10 mlvolumetric flask, diluting to the level mark with methylene chloride,and mixing until the sample is fully dissolved.

The HPLC system used in the HPLC method included a HPLC pump, athermostated HPLC column compartment, HPLC fluorescence detector, andPC-based chromatography data acquisition system. The particular systemdescribed is based on an Agilent 1200 HPLC with ChemStation software.The HPLC column was a Phenomenex Luna C8(2) 150×4.6 mm 5 μm 100 Å, P/N00F4249E0.

The following system settings were used in performing the analyses:

Pump flow=1.0 ml/min

Maximum pressure=200 bars

Fluorescence wavelength: 225 excitation 313 emission: Gain=9

Column Thermostat temperature=25 C

Injection Size=1 μL of diluted sample

Elution type: Gradient, reverse phase

Gradient: 0-7 min 85/15 methanol/water switching to 100% methanol lineargradient.

Run time: 17 minutes

The resulting chromatograph typically contains several peaks. Peaks dueto the free unsulfurized alkylhydroxyaromatic compound (i.e., TPP)typically elute together at early retention times; whereas peaks due tosulfurized alkylhydroxyaromatic compounds typically elute at longerretention times. For purposes of quantitation, the area of the singlelargest peak of the free unsulfurized alkylhydroxyaromatic compound andits unsulfurized metal salt was measured, and then that area was used todetermine the concentration of the total free unsulfurizedalkylhydroxyaromatic compound and its unsulfurized metal salt species.The assumption is that the speciation of alkylhydroxyaromatic compoundsdoes not change; if something does change the speciation of thealkylhydroxyaromatic compounds, then recalibration is necessary.

The area of the chosen peak is compared to a calibration curve to arriveat the wt-% of free alkylphenol and free unsulfurized salts ofalkylphenols. The calibration curve was developed using the same peak inthe chromatograph obtained for the free unsulfurizedalkylhydroxyaromatic compound used to make the phenate product.

The following non-limiting examples are illustrative of the presentinvention.

The degree of high temperature detergency and thermal stability wasevaluated for each of the following examples using the Komatsu Hot Tube(“KHT”) test as described below. The results for each of the examplesare set forth in Table 1.

Komatsu Hot Tube (KHT) Test

The Komatsu Hot Tube test is a lubrication industry bench test thatmeasures the detergency and thermal and oxidative stability of alubricating oil. Detergency and thermal and oxidative stability areperformance areas that are generally accepted in the industry as beingessential to satisfactory overall performance of a lubricating oil.During the test, a specified amount of test oil is pumped upwardsthrough a glass tube that is placed inside an oven set at a certaintemperature. Air is introduced in the oil stream before the oil entersthe glass tube, and flows upward with the oil. Evaluations of the marinediesel cylinder lubricating oils were conducted at temperatures between300-330 degrees Celsius. The test result is determined by comparing theamount of lacquer deposited on the glass test tube to a rating scaleranging from 1.0 (very black) to 10.0 (perfectly clean). The result isreported in multiples of 0.5. Blockage is a deposition in which case thelacquer is very thick and most of the glass test tube is blocked,preventing normal oil and air flow through the test tube. Althoughblocking can be considered a result inferior to a 1.0 rating, itsoccurrence can be greatly influenced by blocking of other test tubesthat are simultaneously tested in the same test run.

The following components are used below in formulating a marine dieselcylinder lubricating oil composition.

Chevron 600N RLOP: Group II-based lubricating oil was Chevron 600N RLOPbasestock, available from Chevron Products Company (San Ramon, Calif.).

ExxonMobil CORE® 2500BS: Group I-based lubricating oil was ExxonMobilCORE®2500BS basestock, available from ExxonMobil (Irving, Tex.).

The detergents used in the examples in Table 1 are described below:

Detergent A: An oil concentrate of a neutral (non-overbased) calciumalkylhydroxybenzoate additive, having an alkyl substituent derived fromC₂₀ to C₂₈ linear olefins, prepared according to the method described inExample 1 of US Patent Application 2007/0027043, but without thesubsequent overbasing step. This additive concentrate contained 2.17 wt.% Ca and about 43.0 wt. % diluent oil, and had a TBN of 61. On an activebasis, the TBN of this additive (absent diluent oil) is 107.

Detergent B: An oil concentrate of an overbased sulfurized calciumphenate derived from propylene tetramer. This additive contained 9.6 wt.% Ca, and about 31.4 wt. % diluent oil, and had a TBN of 260. DetergentB is believed to have a total TPP content, i.e., TPP and itsunsulfurized metal salt, of from about 5 to 7 wt. %, based on the weightof the detergent as manufactured.

Detergent C: An oil concentrate of an unsulfurized, non-overbasedalkylhydroxybenzoate-containing, phenol-distilled additive, having analkyl substituent derived from about 50 wt. % C₂₀ to C₂₈ linear olefinsand 50 wt. % branched hydrocarbyl radical propylene tetramer, preparedaccording to the method described in Example 1 of US Patent Application2004/0235686. This additive contained 5.00 wt. % Ca, and about 33.0 wt.% diluent oil, and had a TBN of 140. On an active basis, the TBN of thisadditive (absent diluent oil) is 210. Detergent C is believed to have atotal TPP content, i.e., TPP and its unsulfurized metal salt, of fromabout 2 to 3 wt. %, based on the weight of the detergent asmanufactured.

Detergent D: An oil concentrate of an overbased calciumalkylhydroxybenzoate additive, having an alkyl substituent derived fromC₂₀ to C₂₈ linear olefins, prepared according to the method described inExample 1 of US Patent Application 2007/0027043. This additive contained5.35 wt. % Ca, and about 35.0 wt. % diluent oil, and had a TBN of 150.On an active basis, the TBN of this additive (absent diluent oil) is230.

Detergent E: An oil concentrate of an overbased calciumalkylhydroxybenzoate additive, having an alkyl substituent derived fromC₂₀ to C₂₈ linear olefins, prepared according to the method described inExample 1 of US Patent Application 2007/0027043. This additive contained12.5 wt. % Ca, and about 33.0 wt. % diluent oil, and had a TBN of 350.On an active basis, the TBN of this additive (absent diluent oil) is522.

Detergent F: An oil concentrate of an overbased calcium alkyltoluenesulfonate detergent; wherein the alkyl group is derived from C₂₀ to C₂₄linear alpha olefins. This additive concentrate contained 16.1 wt. % Ca,and about 38.7 wt. % diluent oil, and had a TBN of 420. On an activebasis, the TBN of this additive (absent diluent oil) is 685.

Detergent G: An oil concentrate of an overbased calciumalkylhydroxybenzoate additive, having an alkyl substituent derived fromC₁₄ to C₁₈ linear alpha olefins. This additive contained 6.25 wt. % Ca,and about 41.0 wt. % diluent oil, and had a TBN of 175. On an activebasis, the TBN of this additive (absent diluent oil) is 296.

Examples 1-3 and Comparative Examples A-J

The marine diesel engine lubricating oil compositions of Examples 1-3and Comparative Examples A-J were prepared as set forth below inTable 1. Each marine diesel engine lubricating oil composition ofExample 1 and Comparative Examples A-J were a SAE 40 viscosity gradeoil, having a kinematic viscosity of about 14.5 cSt @ 100° C., and a TBNof 40 mg KOH/g. Example 2 was a SAE 50 viscosity oil, having a kinematicviscosity of about 18.7 cSt @ 100° C. and a TBN of about 70 mgKOH/g.Example 3 was a SAE 50 viscosity oil, having a kinematic viscosity ofabout 18.9 cSt @ 100° C. and a TBN of about 20 mgKOH/g. The marinediesel engine lubricating oil compositions of Examples 1-3 andComparative Examples A-J were formulated using a major amount of GroupII basestock and a minor amount of a Group I basestock, a detergentcomposition as defined in Table 1, and 0.04 wt. % foam inhibitor.Comparative Example D further comprised 0.57 wt. % of an oil concentrateof a bissuccinimide dispersant derived from 1000 MW polyisobutylenesuccinic anhydride (PIBSA) and heavy polyamine (HPA)/diethylene triamine(DETA), having about 31.7 wt. % diluent oil. Each of the marine dieselcylinder lubricating oil compositions of Examples 1-3 contained no TPPand its unsulfurized metal salt.

TABLE 1 Examples 1 2 3 A B C D E F G H I J Components Chevron 600N 79.049.0 47.0 84.34 80.82 78.33 84.03 82.71 78.16 78.0 72.23 81.16 72.69RLOP, wt % Esso 150 Neutral, — — — — — — — 1.78 — — 8.95 0.95 5.18 wt %Esso Core 2500 9.0 31.0 45.0 — 9.72 10.43 2.81 — 7.26 3.74 — — — brightstock, wt % Detergent A, wt % — — — — — — — — — 8.42 — — 8.42 DetergentB, wt % — — — 15.62 — — 7.81 — — — 11.71 11.71 13.67 Detergent C, wt % —— — — — — — 7.07 — — 7.07 — — Detergent D, wt % — — — — — — — — 6.14 — —6.14 — Detergent E, wt % — — — — — 11.20 — 8.40 8.40 9.80 — — —Detergent F, wt % 7.06 14.12 2.35 — 9.42 — 4.71 — — — — — — Detergent G,wt % 5.71 5.71 5.71 — — — — — — — — — — Foam Inhibitor 0.04 0.04 0.040.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 TBN mgKOH/g 40 70 2040 40 40 40 40 40 40 40 40 40 Test Result KHT @ 300 C. Rating Not runNot run 8.5 7.5 9.0 4.0 8.5 8.0 6.5 7.0 9.0 8.0 7.5 KHT @ 310 C. Rating7.5 Not run 8.5 5.0 2.5 2.5 6.5 4.5 4.5 5.5 6.0 5.5 6.5 KHT @ 315 C.Rating 7.5 8.5 8.5 4.5 blocked blocked blocked 4.0 4.0 4.5 6.0 4.5 5.5KHT @ 320 C. Rating blocked 8.5 8.5 4.0 NA blocked blocked blockedblocked blocked 4.5 blocked blocked KHT @ 325 C. Rating nvt blocked NAblocked NA NA NA NA NA NA 4.5 NA NA KHT @ 330 C. Rating nvt nvt NA NA NANA NA NA NA NA blocked NA NA

As the results set forth in Table 1 show, the marine diesel cylinderlubricating oil compositions of Examples 1-3, which contain theinventive detergent composition, exhibited surprisingly improveddetergency performance over the marine diesel cylinder lubricating oilcompositions of Comparative Examples A-J. This is illustrated by higherKHT values which were sustained over higher temperature ranges,indicating that the marine diesel cylinder lubricating oil compositionsof Examples 1-3 exhibit excellent detergency and thermal stability inthe hot tube test in that they produce little lubricating oil oxidationor degradation product to defile the tube. In addition, Examples 1-3 aresubstantially free of TPP and its unsulfurized metal salt.

It will be understood that various modifications may be made to theembodiments disclosed herein. Therefore the above description should notbe construed as limiting, but merely as exemplifications of preferredembodiments. For example, the functions described above and implementedas the best mode for operating the present invention are forillustration purposes only. Other arrangements and methods may beimplemented by those skilled in the art without departing from the scopeand spirit of this invention. Moreover, those skilled in the art willenvision other modifications within the scope and spirit of the claimsappended hereto.

1-20. (canceled)
 21. A marine diesel cylinder lubricating oilcomposition comprising (a) a major amount of one or more Group IIbasestocks, and (b) a detergent composition comprising (i) 0.1 to 35 wt.% on an actives basis of one or more alkaline earth metal salts of analkyl-substituted hydroxyaromatic carboxylic acid having a total basenumber (TBN) greater than 250, based on the total weight of the marinediesel cylinder lubricating oil composition, and (ii) 0.1 to 34 wt. % onan actives basis of one or more high overbased alkyl aromatic sulfonicacids or salts thereof, based on the total weight of the marine dieselcylinder lubricating oil composition; wherein the aromatic moiety of thealkyl aromatic sulfonic acids or salts thereof contains no hydroxylgroups; wherein the marine diesel cylinder lubricating oil compositionhas a TBN of 5 to 120; wherein the one or more high overbased alkylaromatic sulfonic acids or salts thereof have a TBN of greater than 250;and wherein TBN is measured in accordance with ASTM Standard No. D2896or an equivalent procedure.
 22. The marine diesel cylinder lubricatingoil composition according to claim 21, having a TBN of from 20 to 100.23. The marine diesel cylinder lubricating oil composition according toclaim 21, having a TBN of from 10 to
 40. 24. The marine diesel cylinderlubricating oil composition according to claim 21, which contains lessthan 1.5 wt. % of tetrapropenyl phenol (TPP) and its unsulfurized metalsalt.
 25. The marine diesel cylinder lubricating oil compositionaccording to claim 21, wherein the one or more alkaline earth metalsalts of an alkyl-substituted hydroxyaromatic carboxylic acid are one ormore calcium salts of an alkyl-substituted hydroxyaromatic carboxylicacid.
 26. The marine diesel cylinder lubricating oil compositionaccording to claim 21, wherein the alkyl-substituted moiety of thealkaline earth metal salt of an alkyl-substituted hydroxyaromaticcarboxylic acid is a C₁₀ to C₄₀ alkyl group.
 27. The marine dieselcylinder lubricating oil composition according to claim 21, wherein theone or more alkaline earth metal salts of an alkyl-substitutedhydroxyaromatic carboxylic acid have a TBN greater than 250 and up to800.
 28. The marine diesel cylinder lubricating oil compositionaccording to claim 21, wherein the one or more high overbased alkylaromatic sulfonic acids or salts thereof are one or more high overbasedalkaline earth metal alkyl aromatic sulfonates.
 29. The marine dieselcylinder lubricating oil composition according to claim 21, wherein theone or more high overbased alkyl aromatic sulfonic acids or saltsthereof are one or more high overbased calcium alkyl aromaticsulfonates.
 30. The marine diesel cylinder lubricating oil compositionaccording to claim 21, further comprising one or more marine dieselcylinder lubricating oil composition additives selected from the groupconsisting of an antioxidant, ashless dispersant, detergent, rustinhibitor, dehazing agent, demulsifying agent, metal deactivating agent,friction modifier, pour point depressant, antifoaming agent, co-solvent,corrosion-inhibitor, dyes, extreme pressure agent and mixtures thereof.31. The marine diesel cylinder lubricating oil composition according toclaim 21, which contains less than 0.5 wt. % of any dispersants and/orzinc compounds.
 32. A method for lubricating a marine two-strokecrosshead diesel engine, wherein the method comprises operating theengine with a marine diesel cylinder lubricating oil compositionaccording to claim
 21. 33. The use of a marine diesel cylinderlubricating oil composition according claim 21 for improving hightemperature detergency and thermal stability in a two-stroke crossheadmarine diesel engine.